SU649308A3 - Method of obtaining triazapentadiene derivatives or salts thereof - Google Patents

Description

one

This invention relates to a process for the preparation of triazapentadiene derivatives not described in the literature, which possess biological activity and can be used in agriculture.

The literature describes the interaction of amines with derivatives of hydrocyanic acid, such as isonitriles l.

The purpose of the invention is to develop a process for the preparation of previously unknown derivatives of triazapentadiene or their salts with high biological activity.

This is achieved according to the described process for the preparation of triazapentadienes, which is based on a known reaction.

According to the invention, a process for the preparation of new derivatives of triazapentadiene of general formula I

"L SN S

HF

where RJ is alkyl with 1-4 carbon atoms,

 - hydrogen, halogen or alkyl with 1-4 carbon atoms,

Rg is cyclopengyl or cyclohexyl, or methyl or ethyl, substituted cyclopentyl or cyclohexyl, or phenyl, which may be substituted by one or two alkyl or alkoxy groups with 1-4 carbon atoms,

 - hydrogen or alkyl with 1-4 carbon atoms, or their salts,

concluding that formamidine of the formula II R —VI — C — KIH — CH, I

where Rj (is a group of the formula I

20

where Rj and Rg have the indicated meanings and R is hydrogen or Rj (- having the meanings of the radical RJ and R having the indicated meanings. is reacted with an isonigram of formula IV Rj (NC, where Rj (meaning of the radical R or RX is a group of formula III, in medium an inert organic solvent in the presence of copper oxide as a catalyst at 50-80 ° C with the following extraction of the target product in free form or salt transfer, using for this purpose acids such as maleic or citroxylic. benzene or toluene. The desired product is isolated by known methods, for example, by distillation under vacuum or by recrystallization. Example 1. A. A mixture consisting of N, 4-dimethylphenyl-N-methylformamidine (3.0 g; 0, O185 mol), isonitrile cyclohexane (2.01 g; 0.0185 mol), benzene (60 ml) and monovalent copper oxide (trace amount) are heated for 2 hours at reflux temperature. The release of methylamine is observed and the heating is immediately stopped. The reaction mixture was kept at room temperature for nine days, after which it was analyzed by thin layer chromatography, which showed that a significant amount of amidine still remained in the reaction mixture. The mixture is then heated for 8 hours at 70 ° C, after which the results of thin layer chromatography show that a small amount of amidine still remains. After standing overnight, the reaction mixture is heated at about 70 ° C for six hours, filtered and concentrated in vacuo to give a dark red oil (4.7 g) in a residue. The dark red oil is purified by treatment with neutral alumina in petroleum ether with a boiling point. 40-60 ° C. After evaporation of either petroleum ether in vacuo, an almost colorless oil is obtained which crystallizes on aging to form large colorless prisms of 1-piclohexyl-5- (2,4-dimethylphenyl) -3-methyl-1,3,5-triazapent-1, 4 -diene, melted at 55-57.5C. Found,%: C 75.60; H 9.40; N 15.59 Calculated,%: C 75.24; H 9.29; N 15.48 B. Monomealeic salt of the compound, the preparation of which was described in reamer 1A, is obtained by dissolving the above compound (2.5 g) in diethyl ether (50 ml) with the addition of the solution to the floating solution of maleic acid (1.16 d) in diethyl ether (100 ml). The white precipitate formed, the mono maleic salt of 1-cyclohexyl-5- (2.4, methylphenyl) -3-methyl-1,3, 5-triazapentane-1,4-diene (2.6 g) 7 has a mp. 126, (with decomposition). B. Monocitraconate, tartrate, and di-p-halo tartrate — the salts of the compounds described in Example 1A are also prepared in a manner similar to the method of Example 1B; melting point of ditroconic salt 128 129 ° C. Found,%: C 66.09; H 7.82; N 10.19. C | 7H25 O 04 Calculated,%: C 65.83; H 7.73; N 10.47 Examples 2-12. Similarly to the method of Example 1, using N - (2,4-dimethylphenyl) -N-methylformamidine or N- (4-chloro-2-methylphenyl) -X-methylformamidine and the corresponding isonitrile as the starting compounds, the compounds shown in Table 1 are obtained. Example 13 A. A. Cyclohexylamine (10.5 g; 0.105 mol) was added to a solution of methyl N-methylacetimidate (8.7 g; 0.1 mol) in toluene (EOm). After 72 hours of aging at normal room temperature and heating for 32 hours at 6 ° -70 ° C, the solvent is removed by evaporation to obtain an oil that crystallizes on standing. When the chromatography is carried out by the scientific research institute from alumina using diethyl ether as an eluene, N-cyclohexyl-N-methyladamidine is obtained as a colorless solid product (til g), melting at 108.5-109 ,. Found,%: C, 70.22; H 11.92; N 17.92. Cp H | gN2 Calculated,%: C 70.08; H 11.76; N 18.15 B. A solution of N-cycla-hexyl-X.4 v-chiacetamide prepared analogously to example 564 of the example ISA (4.11 g; 0.027 mol), and 2,4-dimethylphenylisonigril (3.88 g; 0.03 mol) in anhydrous toluene (ZOml) in the presence of a trace amount of monovalent copper oxide is kept at room temperature for 150 hours, heated at 80-85 ° C for 14 hours, and then at reflux temperature for 2 hours and 30 minutes. The reaction time is monitored by NMR spectroscopy. The resulting dark red solution is filtered through alumina. concentrated to obtain an oil (7.5 g), which partially solidifies on aging to form an oily solid product, from which, upon rubbing on a porous plate, the target compound is formed — 1-1 chlohexyl-2,3.methyl-5- (2.4 - -dimethylphenyl) -1,3,5-triazapent-1,4-diene, melting at 37-39 ° C; The molecular weight of this compound based on mass spectrometry data is 285. Found: C, 75.77; H 9.60; Calculated,%: C 75.75; H 9.54; W 14.72. B. Nitracones A triazapent-1,4-diene salt, the preparation of which was described in Example 13B, is prepared by adding a solution of citraconic acid (260 mg 0.002 mol) in anhydrous diethyl ether (10 ml), added dropwise at room temperature to a solution of the indicated triazapenta-1,4-diene (570 mg; 0.002 mol) in anhydrous diethyl ether (10 ml). The resulting precipitate of 1-cyclohexyl-2,3-dimethyl-5- (2,4-dimethyl-phenyl) -l, 3,5-tri-triazapent-1, 4-yiena mono-citraconate (770 mg), melted at 1 O 10 -3 C, is filtered and crystallized from ethyl acetate / petroleum ether with so Kip. 4060 ° C. Found,%: C 66.34; H 8.12; K 9.97 Calculated,%: C, 66.48; H 8.01; N 10.11. The free base of the triazapent-1,4-diene can be isolated from the citracon salt by treating, for example, with triethylamine in diethyl ether. Examples 14, 15. According to the method described in Example 13B, the compounds shown in Table 2 are prepared using the corresponding amides and 2,4-dimethylphenylisonitrile. 2, Table 1 NR,

Cyclopentyl

2 СНсесеЦиклогексил

SRCyclopentyl

СНг-СНг5 CHj6 С— (iH, j- f VcHz-ai2 у

257

16.25

9.10 16.33)

9.01

79-80

7.60

14.27 14.39)

7.60

277

7.44

13.44 15.12)

7.26

8.29

12.41 307 13.67)

8.20

327

12.81

6.68

12.82) 6.76

M.p.

R:

;

° s

I

7 ee-sch 7-Ng-SNgSNzO

8 se- (

Continued table. one

Molecules p) -

Analysis, weight on

found (calculated) by the base of the mass;

N

H

With thunder

64.43 6.6311.73 373

(64.25 6.47a, 24)

67.01 8.0913.77 305

(66.76 7.9113.74)

6.65 (5, ЗН) Н2СНа

7.5 (g, 2H) 229

8.9 (t, 3N)

1 7.74

VCH,

7.7 (5) t 1.8

N: H-M-CH,

51HOC W1600,1620 cm

Claims (2)

i, r. Claim 1. Method for the preparation of derivatives of gazapengadiene common formula I - ,, N 15-Of ri to x JI I lif where RJ is alkyl with 1-4 atoms carbon R2 - hydrogen, halogen or alkyl with 1-4 atoms carbon, RJ is cyclopentyl or cyclohexyl, or methyl or ethyl, substituted by cyclopyl or cyclohexyl group, or phenyl group, which may be substituted by one or two alkyl or alkoxy groups with 1-4 carbon atoms, R is hydrogen or alkyl with 1 -4 carbon atoms, or their salts, characterized in that formamidine II NH-CH, 810, where R is a group of the formula Advantages and - hydrogen or R has the meaning of the radical Rg and Rj has the indicated meanings, is reacted with an ionitrile of formula IV jR ,, where R has the meaning of radical 1. or Rj, is a group of formula III, in the environment of an inert organic solvent B in the presence of catalyst recording copper when BS-BO with the subsequent selection of the target product in free form or in the form of salt, 2. The method according to claim 1, about 11 and 11, and so that benzene or toluene is used as an inert organic solvent. Sources of information, receive your attention during examination 1. Weigand-Hilgegagh. Experimental Methods in Organic Chemistry, L., Xi 1968, p. 375,